Iodine → tert-Butyl 5-(tert-butyldiphenylsilanyloxy)-3-{5-[3-(2-ethylbutyl)cyclobutyl]-4-iodoisoxazol-3-yl}valerate

HRID 1912096Notes

Reaction equation

HRID 1912096 reaction equation
[Si:1]([O:18][CH2:19][CH2:20][CH:21]([C:30](=[N:43][O:44]C)[C:31]#[C:32][CH:33]1[CH2:36][CH:35]([CH2:37][CH:38]([CH2:41][CH3:42])[CH2:39][CH3:40])[CH2:34]1)[CH2:22][C:23]([O:25][C:26]([CH3:29])([CH3:28])[CH3:27])=[O:24])([C:14]([CH3:17])([CH3:16])[CH3:15])([C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C(#N)C.[I:49]I.S([O-])([O-])(=O)=S.[Na+].[Na+]>C(OCC)(=O)C>[Si:1]([O:18][CH2:19][CH2:20][CH:21]([C:30]1[C:31]([I:49])=[C:32]([CH:33]2[CH2:36][CH:35]([CH2:37][CH:38]([CH2:41][CH3:42])[CH2:39][CH3:40])[CH2:34]2)[O:44][N:43]=1)[CH2:22][C:23]([O:25][C:26]([CH3:28])([CH3:27])[CH3:29])=[O:24])([C:14]([CH3:17])([CH3:15])[CH3:16])([C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

6

Reactant 4

HCID 807IodineHCID 6342AcetonitrileHCID 24477Sodium Thiosulfate2×HCID 86675053tert-Butyl 3-[2-(tert-butyldiphenylsilanyloxy)ethyl]-6-[3-(2-ethylbutyl)cyclobutyl]-4-methoxyimino-5-hexynoate

Product 1

HCID 71127336tert-Butyl 5-(tert-butyldiphenylsilanyloxy)-3-{5-[3-(2-ethylbutyl)cyclobutyl]-4-iodoisoxazol-3-yl}valerateYield 80.4%

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Procedure

tert-Butyl 3-[2-(tert-butyldiphenylsilanyloxy)ethyl]-6-[3-(2-ethylbutyl)cyclobutyl]-4-methoxyimino-5-hexynoate (7.50 g) and acetonitrile (60 mL) were mixed. To the mixture was added iodine (7.54 g) was added at ice temperature. The mixture was stirred for 4.5 hr, and then to the mixture were added aqueous 5 w/v % sodium thiosulfate (50 mL), ethyl acetate (200 mL) and aqueous 5 w/v % sodium thiosulfate (75 mL, 150 mL) at ice temperature. The aqueous layer was removed, and the organic layer was washed with saturated aqueous sodium bicarbonate/brine=1/1 (100 mL) and brine (50 mL), then dried over sodium sulfate. The sodium sulfate was filtered off and the filtrate was concentrated in vacuo. The resultant residue was purified twice by silica gel column chromatography (Eluent: ethyl acetate/hexane=1/50→1/40→1/20) to give the title compound (7.1 g).

Workup

  1. additionwas added at ice temperature
  2. customThe aqueous layer was removed
  3. washthe organic layer was washed with saturated aqueous sodium bicarbonate/brine=1/1 (100 mL) and brine (50 mL)
  4. dry with materialdried over sodium sulfate
  5. filtrationThe sodium sulfate was filtered off
  6. concentrationthe filtrate was concentrated in vacuo
  7. customThe resultant residue was purified twice by silica gel column chromatography (Eluent: ethyl acetate/hexane=1/50→1/40→1/20)

Sources & evidence

ORD record
ord-2a7c132093984180a87ae511a7ffa10d
Source dataset
uspto-grants-2013_12
Patent number
US08604069B2

Reaction notes

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